ORGANIC
LETTERS
2
003
Vol. 5, No. 11
887-1890
Synthesis of a [2]Catenane around a
2+
1
Ru(diimine) Scaffold by Ring-Closing
3
Metathesis of Olefins
‡
Fabio Arico, Pierre Mobian, Jean-Marc Kern,* and Jean-Pierre Sauvage*
Laboratoire de Chimie Organo-Min e´ rale, UMR 7513 du CNRS, UniVersit e´ Louis
Pasteur, Facult e´ de Chimie, 4, rue Blaise Pascal, 67070 Strasbourg Cedex, France
Received March 11, 2003
ABSTRACT
The synthesis of a ruthenium[2]catenane is described. One ring includes two 1,10-phenanthroline moieties, the other a bipyridinic unit. The
interlocking ring system was formed by using a double ring closing metathesis reaction. Under irradiation, a rapid and selective decoordination
of the bipyridinic fragment was observed, leading to a new catenane in which the metal is only coordinated to the bis-phenanthroline moiety.
Among the numerous catenanes and rotaxanes elaborated in
the course of the last two decades,1-6 those synthesized with
use of transition metals as templates represent a special
family, with particularly interesting properties originating
from the electro- and photochemical reactivity of the central
metal complex.
Copper(I) has been used extensively as a gathering and
templating center in the past for preparing various catenanes.
7
Very recently, our group has also proposed using a Ru-
‡
Present address: Chemistry Departement, Reading University, Whitek-
2+
(
diimine)
3
complex as a scaffold to construct rotaxanes
nights, Reading, RG6 6AD, UK.
8
,9
(1) For the early work on catenanes and related species carried out in
and catenanes with, in particular, the aim of making light-
driven molecular machines.
Freiburg (Germany), see: Schill, G. Catenanes, Rotaxanes and Knots;
Academic Press: New York, 1971. Some particularly representative more
recent contributions are listed in refs 2-6.
Since the ring-closing metathesis (RCM) reaction of
olefins turned out to be extremely efficient for preparing
(2) Molecular Catenanes and Knots; Sauvage, J. P., Dietrich-Bucheker,
C. O., Eds.; Wiley: New York, 1999.
3) Chambron, J.-C.; Dietrich-Bucheker, C. O.; Sauvage, J.-P.; Supramo-
1
0
copper(I)-based catenanes and knots, we applied the
(
2
+
lecular Chemistry; Lehn, J.-M., Ed., Pergamon:Elsevier Science Ltd.: New
York, 1996; Vol. 9, pp 43-63.
same methodology to Ru(diimine)
-based systems. The
3
(
(
4) Amabilino, D. B.; Stoddart, J. F. Chem. ReV. 1995, 95, 2725-2828.
5) (a) Hunter, C. A. J. Am. Chem. Soc. 1992, 114, 5303-5311. (b)
(7) (a) Dietrich-Buchecker, C. O.; Kern, J. M.; Sauvage, J. P. J. Am.
Chem. Soc. 1989, 111, 7791-7800. (b) Livoreil, A.; Sauvage, J. P.;
Armaroli, N.; Balzani, V.; Flamigni, L.; Ventura, B. J. J. Am. Chem. Soc.
1997, 119, 12114-12124.
(8) Pomeranc, D.; Heitz, V.; Chambron, J.-C.; Sauvage, J. P. J. Am.
Chem. Soc. 2001, 123, 12215-1221.
V o¨ gtle, F.; D u¨ nnwald, T.; Schmidt, T. Acc. Chem. Res. 1996, 29, 451-
4
60 and references therein. (c) Johston, A. G.; Robin, J.; Leigh, D. A.
Angew. Chem., Int. Ed, Engl. 1995, 34, 1209-1216.
6) Transition metal-incorporating catenanes: (a) Ogura, K.; Hagihara,
(
H.; Ibukuro, F.; Fujita, M. Nature 1994, 367, 720-723. (b) Kim, K. Chem.
Soc. ReV. 2002, 31 (2), 96-107. (c) McArdle, C. P.; Irwin, M. J.; Jennings,
M. C.; Vittal, J. J.; Puddephatt, R. J. Chem. Eur. J. 2002, 8, 723-734.
(9) Mobian, P.; Kern, J.-M.; Sauvage, J.-P. J. Am. Chem. Soc. 2003,
125, 2016-2017.
1
0.1021/ol0300367 CCC: $25.00 © 2003 American Chemical Society
Published on Web 05/09/2003